Carole A. LeBlanc, Ph.D.Chemical and Material Risk Management (CMRM) Directorate

Office of the Deputy Under Secretary of Defense for Installations and EnvironmentTel.: 703-604-1934 For DoD EHS ‘Nano’ Work Group information Email: carole.leblanc@osd.mil

Introduction to Nanotechnology for Defense Environment, Health & Safety (EHS)

and Research Professionals in Support ofthe Acquisition Process

March 28, 2011DoD Environmental Monitoring and Data Quality (EMDQ) Workshop

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Nanotechnology 101 Course Outline

Overview of DoD CMRM Introduction to Nanotechnology (this briefing) Includes the status of local, federal and international regulation

» What science and technology (S&T) and acquisition specialists need to know

Plan: National Nanotechnology Initiative (NNI) 2011 EHS Research StrategyPractice: The Defense Mission and Nanomaterials EHS Research Case Studies from Subject Matter Experts (SMEs)

throughout the Services and CMRM update on nanomaterials» Problem statement» Research goals and objectives» Results and observations» Conclusions

• Future research needs» Additional resources, references, etc. 2

Some ‘Wiki-like’ DefinitionsFor educational purposes only

Nanotechnology (‘nanotech’) is the study of manipulating matter on an atomic and molecular scale. In general, nanotechnology deals with structures sized between 1 to 100 nanometers (nm), i.e., at the ‘nanoscale’ in at least one dimension, and involves developing materials or devices within that size. Quantum mechanical effects are very important at this scale.

Nanoengineering is the practice of engineering at the nanoscale.

Nanomaterials is the field that takes a materials science-based approach to nanotechnology. It studies materials with morphological features on the nanoscale, and especially those that have special properties stemming from their nanoscale dimensions such as large surface area.

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How Small Is Small?Very Small!

George Whitesides, Chemistry and Chemical Biology Department, Harvard University, Cambridge, MA 4

Concept in, “There’s Plenty of Room at the Bottom,” a talk given by Richard Feynman, American Physical Society, Caltech, 1959 Gravity would become less important, and

Surface tension and van der Waals attraction would become more important

Term first defined by Norio Taniguchi, Tokyo Science University, 1974 Further refined by K. Eric Drexler by 1986 in his books

» Engines of Creation: The Coming Era of Nanotechnology» Nanosystems: Molecular Machinery, Manufacturing, and

Computation 5

History of NanotechnologyNot actually a ‘new’ science

Development of Nanotechnology

www.foresight.org 6

Chemical and Material Risk Management Directorate www.denix.osd.mil/MERIT

1959- Famous Richard Feynman talk

on molecular machines Caltech

1985- Buckyball discovered by Kroto,

Smalley, Kurl 2000- President Clinton announces plans for NNI

1974- Term "nanotechnology" first

used by Norio Taniguchi

\

1991 -Carbon nanotube discovered by Sumio

liji a

~50 1960 1970 1980 Year

2010

1931- First electron

microscope built by Ruska

and Knoll 1977- Eric Drexler

originates concept of molecular

nanotechnology at MIT

1997-Zyvex, first "nanotech" company

2001 -Institute for Soldier Nanotechnology, MIT

History and Development of Nanotoxicology

Courtesy of Jeff Steevens, ACoE7

Chemical and Material Risk Management Directorate www.denix.osd.mil/MERIT

Ultra fine particles

~50

1713- Ramazzini described black 197 4- First GMO

lung disease mouse created by Jaenisch

Diesel exhaust

Engineered NP _____ _,.? •

GMO Technology

1985- Oberdorster described inhalation

toxicity of Ti02

2003-lssue recognized by EPA, NIOSH,

other agencies 2004- California pass broad ban on

GMO products

Growing Body of EHS Research Far-reaching implications or singular exceptions?

Nanoparticles induced skin aging in mice through oxidative stress (Chinese study, 2009)

Nano-titanium dioxide (TiO2) consumed by mice linked to DNA and chromosome damage (two-year UCLA School of Public Health study)

Some forms of carbon nanotubes may be as harmful as asbestos, if inhaled in sufficient quantities (major study published in Nature Nanotechnology)

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Consequences and ConcernsA few examples

INTENDED CONSEQUENCES

Passing through the blood brain barrier or placentaIn vivo drug delivery

Bioremediation (only one illustration of an intended environmental release)

Antimicrobial activity

POTENTIAL UNINTENDED CONSEQUENCES

Passing through the blood brain barrier or placentaInterference with other biological pathways (for example, enzymatic activity)Little understood fate and transport mechanisms could lead to deleterious ‘sinks’ and cumulative effectsInability to differentiate between beneficial and harmful bacteria

WE STILL DON’T KNOW WHAT WE DON’T KNOW.

Kinds of Nanomaterials

Nanoparticles

Fullerenes

Nanotubes

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A researcher harvests single-walled nanotubes from a carbon arc reactor. Source: National Nanotechnology Initiative 2011 EHS Research Strategy.

Properties exploited by artists as early as the 9th century ‘Glitter’ paint

Synthesis Attrition

» Macro- or micro-scale particles are ground in a ball mill or other size-reducing mechanism

Pyrolysis» A vaporous precursor (liquid or

gas) is forced through an orifice at high pressure and burned

Thermal plasma» Delivers the energy necessary to

cause evaporation of the mm-size particlesModern applications involve quality control (QC) issues of uniformity and agglomeration 11

NanoparticlesUsed as powders, in sol gel, colloids, etc.

Microscopic images of mesoporous silica nanoparticles of various diameters.  

Unique Properties of Nanoparticles

MACROSCALE PROPERTY

Aluminum: Stable

Copper: Opaque

Gold: Insoluble

NANOSCALE PROPERTY

Aluminum: Combustible

Copper: Transparent

Gold: Soluble

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Colloidal CdSe (cadmium selenide) quantum dots

dispersed in hexane. Quantum confinement

effects allow quantum-dot color to be tuned with

particle size.

Courtesy of scientist doing work for the Army as part of the Institute for Soldier Nanotechnology (ISN),Massachusetts Institute of Technology

FullerenesA fullerene is any molecule composed entirely of carbon, in the form of a hollow sphere, ellipsoid, or tube Spherical fullerenes are called buckyballs

Cylindrical fullerenes are called nanotubes

Buckminsterfullerene C60 Carbon nanotube smallest fullerene molecule in which no two 

pentagons share an edge (occurs naturally in soot) 13

Predicted by Eiji Osawa of Toyohashi University of Technology, 1970 Prepared by Richard Smalley, Robert Curl, James Heath, Sean O'Brien, and Harold Kroto at Rice University, 1985 Named in honor of Buckminster Fuller, whose geodesic dome

designs (soccer/volleyball-like) it resembled

Curl, Kroto and Smalley received Nobel Prize in Chemistry for discovery of fullerenes, 1996

» Smalley’s work partially funded by Army Research Organization

Detected recently in outer space According to at least one astronomer, “It’s possible that buckyballs

from outer space provided seeds for life on Earth.”

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Scientific DiscoveryOf the fullerene

Another common fullerine is C70

Fullerenes with 72, 76, 84 and even up to 100 carbon atoms are possible

Smallest fullerene is C20

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Many Sizes/Configurations Of fullerenes possible

Fullerene C70

Single-walled carbon nanotubes (SWCNT)

Multi-walled carbon nanotubes (MWCNT)

Nanobud (obtained by adding a buckminsterfullerene)

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Nanotubes

The longest, the shortest, the thinnest…

Manipulation to impart functionality Important to control

properties such as

» Hardness and strength

» Catalysis

» Chirality

» Superconductivity

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‘Extreme’ Nanomaterials

Electrode materials screening by Ilika Technologies, Chilworth, UK, shows high activity for previously undiscovered alloy.

Preparing NanomaterialsMaterial and molecular perspectives

Larger to smaller Physical phenomena become pronounced as size

decreases» What’s at stake: statistical and quantum mechanical

effects

Simple to complex Molecular self-assembly

» What’s at stake: synthetic chemistry, pharmaceuticals, polymers

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Bottom-up Seeks to arrange smaller components into more complex

assemblies (chemical self-assembly)» DNA nanotechnology utilizing specificity of base-pairing

Top-down Seeks to create smaller devices by using larger ones to direct

their assembly (no atomic-level control)» Giant magnetoresistance-based hard drives

Functional Seeks to develop components of a desired functionality

without regard to assembly methodology» Single-molecule components in nanoelectronic devices

Biomimicry Seeks to apply biological methods and systems found in nature

» Possible use of viruses‘Anticipatory’ approaches include nanorobotics, etc. 19

Preparing NanomaterialsApproaches and illustrations

Megatubes: larger in diameter than nanotubes, and prepared with walls of different thicknesses Potentially used for the transport of a variety of molecules of

different sizes

Fullerites: solid-state manifestation of fullerenes, and related compounds and materials ‘Ultrahard fullerite’ is a term used to describe material produced by

high-pressure high-temperature (HPHT). Such treatment converts fullerite into a nanocrystalline form of diamond which has been reported to exhibit remarkable mechanical properties.

‘Nano onions’: spherical particles based on multiple carbon layers surrounding a buckyball core Proposed for lubricants

Silicon buckyballs Created around metal ions

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Unique Uses

Defense ApplicationsCarbon nanotubes EMI hardened electronics

Lightweight composites

Filtration

Infrared obscurants

Textiles

Reactive coatings

Light weight/hi energy batteries

Metals Reactive/dynamic coatings

Propellants, wear resistant surfaces, reactive coatings (Al)

Sensing

Chemically and BiologicallyProtective Shelter

Natick Soldier Center

Courtesy of Jeff Steevens, ACoE21

Summary of Nanomaterial RegulationU.S. Federal Regulations U.S. State Regulations International Regulations

• U.S. Environmental Protection Agency (EPA) has proposed regulation of nanomaterials through the Toxic Substances Control Act (TSCA)

• With respect to statutes such as the Clean Air Act (CAA) or Clean Water Act (CWA), the USEPA maintains the authority to regulate nanomaterials as pollutants

• California has taken the lead in addressing nanomaterials as an EC, largely through voluntary reporting efforts

• California and several other states have listed nanomaterials as a priority contaminant of concern

• The European Union (EU) is regulating nanomaterials under the Regulation, Evaluation, Authorization, and Restriction of Chemicals (REACH) legislation. Will involve: (1) Labelling to identify products containing nanomaterials; and (2) Listing nanomaterial content in Safety Data Sheets (SDSs), the equivalent of Material Safety Data Sheets (MSDSs) in the U.S.

• Individual countries are also reviewing their regulatory regimes with respect to nanomaterials

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U.S. EPA (as of December 20, 2010)» Test rule for certain nanomaterials, including MWCNT,

under TSCA Section 4(a)

• Intent to issue notice of proposed rulemaking (NPRM) by April 2011

» Proposal to set reporting requirements for certain nanomaterials under TSCA Section 8(a)

• Intent to issue NPRM by February 2011

» 2nd Significant New Use Rule (SNUR) under TSCA Section 5(a)(2)

• Intent to issue NPRM by February 2011

• 1st SNUR on MWCNT and SWCNT went into effect in October 2010

More on U.S. Regulation

More on EU Regulation‘REACH’ was enacted in June 2007 to replace some 40 pre-existing laws Covers all 27 EU Member States and some neighboring states

Focus is on High-volume (most exposure) chemicals Will also require application-specific authorization to use

» Substances of Very High Concern (SVHCs)• Very persistent, very bio-accumulative (vPvB)• Carcinogens, mutagens and reproductive toxins• Risks adequately controlled OR benefits outweigh risks AND

no alternatives existsREACH is far more sweeping than EU’s Restriction of Hazardous Substances (RoHS) Six RoHS-regulated chemicals vs. thousands of chemicals

already REACH-registered 24

RoHS and Lead-free Electronics A cautionary tale

Expected Operational Service Life (Years)

Har

shne

ss o

f Ser

vice

Env

ironm

ent

(Hum

idity

, Tem

pera

ture

, Sho

ck, V

ibra

tion)

Low

High

5 101 203 30

Con

sequ

ence

s of

Fai

lure

Cell PhonesMajor Home Appliances

Cars

SatellitesMedical Equipment

A B

C D

Desktop PCs

Network Servers

Missiles

Aircraft

62%

8% >1%

29%Industrial Products

Tin Whiskers ??

Operating Environment vs. Operational Life-time

Courtesy of E. Morris,Lockheed-Martin

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Effects of REACH on Product InnovationMilitary chemical uses were not considered, and there is no blanket defense exemption Different EU Ministries of Defence have different opinions on

applying REACH to their militaries, and can issue narrow, performance-based exemptions for defense-unique products

Companies might find it economically infeasible to continueproviding these materials, if DoD is the only user

» May mean more expensive defense products

REACH will incentivize companies to develop substitute (i.e., safer and greener) commercial chemicals and materials Some of them will be nanomaterials (also covered by REACH) All of them should require toxicological/environmental testing

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DoD: The Only Federal Agency with a PlanStrategic Plan for REACH signed out by Principal Deputy USD for AT&L1 July 2010

Defense Logistics Agency (DLA) has major role in identifying Service-specific supply concerns

Plan available at www.denix.osd.mil/cmrmd/ChemicalManagement/TSCA.cfm

1 Under Secretary of Defense for Acquisition, Technology and Logistics.27

Goals of DoD’s Strategic Plan for REACH

1. Protect the availability of substances with significant mission impact

2. Ensure the performance of substitutes3. Guard against disruptions to the supply chain 4. Encourage partners to pursue defense exemptions 5. Capitalize on ESH improvements6. Capitalize on chemical management opportunities 7. Assure acquisition strategies 8. Plan for future regulations9. Minimize negative impacts to Foreign Military Sales

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Requirements of a Developing Science

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During the SME presentations, keep in mind Opportunities for professional

growth and career development» For S&T

• What analytical skills and scientific instruments are needed?

» For acquisition

• What skill sets are needed to ensure timely, well-understood and authoritative delivery of this powerful new technology to the Warfighter?

Report available at: www.nano.gov/html/meetings/humanhealth